AbstractA large groundwater system in the Amadeus Basin, central Australia, discharges to a chain of playa lakes 500 km long. The playas contain highly concentrated brines; these are sodium‐chloride rich waters with appreciable magnesium and sulphate and very low concentrations of calcium and bicarbonate. Gypsum, glauberite, and other evaporite minerals are precipitating in the playas. The groundwaters evolve to brine by concurrent processes of dissolution, evaporative concentration, mineral precipitation, and mineralogical change. Chemical evolution is considered with reference to a concentration factor based on chloride. Ion transfer calculations demonstrate losses of magnesium and bicarbonate throughout, as a result of precipitation. Sodium, potassium, calcium, and sulphate are gained initially as a result of dissolution but lost subsequently as a result of precipitation.Larger playas in the chain, exemplified by Lake Amadeus, have dual shallow and deep groundwater flow paths whereas the smaller playas, exemplified by Spring Lake, have only shallow flow paths. Brines in the larger playas are diluted by deep groundwaters and this is reflected in the degree of saturation attained with respect to particular minerals. Thus, saturation with respect to gypsum and glauberite is attained earlier in Spring Lake than in Lake Amadeus. Saturation with respect to halite is attained in Spring Lake but not in Lake Amadeus. Both playas are undersaturated with respect to hexahydrite and sylvite although these minerals occur in efflorescent crusts in Spring Lak